O-alkyl-S-alkyl-O-substituted phenyl-thiophosphoric acid esters

ABSTRACT

Organic phosphoric acid derivatives of the formula   WHEREIN R1 is C3-C5 alkyl, optionally interrupted by oxygen or sulphur, R2 is methyl or ethyl, R3 is alkylcarbonyl, alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl trihaloalkyl, R4 and R5 are each independently hydrogen, C1-C5, alkyl or halogen and X is oxygen or sulphur, their manufacture and their use in pest control.

United States Patent 11 1 Drabek et a].

1 1 June 24, 1975 1 1 O-ALKYL-S-ALKYL-O-SUBSTITUTED PHENYL-THIOPHOSPHORI ACID ESTERS 175] Inventors: Jozef Drabek, Allschwil; Denis Varsanyi, Arlesheim, both of Switzerland [73] Assignee: Ciba-Geigy Corporation, Ardsley,

22 Filed: July 15,1974 [21] App]. No: 488,867

Related U.S. Application Data 162] Division of Scr. No. 292.218, Septv 25, 1972. Pat.

[52] LES. Cl. 260/955; 260/941; 260/943; 260/946; 260/948; 260/950; 424/211; 424/212; 424/214; 244/216; 244/217; 244/225 [51] Int. Cl. AOln 9/36; C07? 9/18 [58] Field of Seareh 260/955 964 [56] References Cited UNlTED STATES PATENTS $725,514 4/1973 Tsuchiya e1 21] 260/964 3319755 6/1974 Tarnow et a1 260/955 3.825636 7/1974 Kishino et a1 1. 260/964 3,839,511 10/1974 Kisl'llnn et a1 260/964 Primary E.ran1inerLorraine A. Weinberger Assistant Examiner-Richard L. Raymond Attorney, Agent, or Firm-Frederick H. Rabin {57] ABSTRACT Organic phosphoric acid derivatives of the formula 3 Claims, N0 Drawings 1 O-ALKYL-S-ALKYL-O-SUBSTITUTED PHENYL-THIOPHOSPHORIC ACID ESTERS This is a division of application Ser. No. 292,218, filed on Sept. 25, 1972, now US. Pat. No. 3,839,509.

This invention relates to new organic phosphoric acid derivatives, their manufacture and their use in pest control.

According to the present invention there are provided compounds of the general formula wherein R is C -C alkyl, optionally interrupted by oxygen or sulphur,

R, is methyl or ethyl,

R is alkylcarhonyl, alkoxycarbonyl, aminocarbonyl,

alkylarninocarbonyl, dialkylaminocurbonyl or trihaloalkyl,

R, and R, are each independently hydrogen, C,-C,-,, alkyl or halogen and is oxygen or sulphur.

Halogen denotes fluorine, chlorine, bromine and/or iodine, especially chlorine and/or bromine.

The alkyl groups R,, R R and R, can be branched or straight chain, substituted or unsubstituted, and in the case of R, and R preferably have 1 to 5 carbon atoms in the chain. Substituents on these groups may be for example halogen, hydroxy, nitro, cyano, alkoxy or alkylthio.

In the scope of the present invention there are, as alkyl groups, for example methyl, methoxyrnethyl, ethyl, ethoxyethyl, propyl, isopropyl, n-,i-, sec-. tertbutyl and n-pentyl. Trihaloalkyl may be for example trifluoromethyl, difluorochloromethyl and fluorodichloromethyl.

On account of their activity, preferred compounds of formula I are those in which R, is n-propyl R is ethyl R is methylcarbonyl, methoxycarbonyl, ethoxycarbonyl, aminocarbonyl, methylaminocarbonyl,

dimethylaminocarbonyl or trifluoromethyl, R, and

R are each hydrogen or chlorine and X is oxygen.

The compounds of formula I may be made by the following methods known per se:

la) X R S u R 1 c1 lb) X 11 8 ll 2O P v I 2 ln formulae ll, ill and IV, R, to R and X have the meanings given for formula I and Me stands for an alkali metal, particularly sodium or potassium, or an ammonium or alkylammonium group.

As acid binding agents there can be used: tertiary ammines, e.g. trialkalyammines, pyridine, dialkylanilines; inorganic bases such as hydrides, hydroxides, carbonates and bicarbonates of alkali and alkaline earth metals. [n the reactions it is sometimes necessary to use catalysts such as e.g. copper or copper chloride. Reactions la and lb are carried out at a reaction temperature of 0 to C at normal pressure and in solvents or diluents inert to the reactants.

Suitable as inert solvents or diluents are, for example ethers and ethereal compounds such as diethyl ether, dipropyl ether, dioxane, tetrahydrofuran; amides such as N,N-dialkylated carboxylic acid amides; aliphatic, aromatic and halogenated hydrocarbons, particularly benzene, toluene, xylene, chloroform, chlorobenzene; nitriles such as acetonitrile; DMSO.

The starting materials of formulae ll, [1], and IV are known and can be made by methods similar to those known, e.g. in J. Org. Chem. 30,3217 (i965).

The compounds of formula I can be used for combating the most varied animal and vegetable pests.

Particularly they are suitable for combating all development stages, e.g. eggs, larvae, pupae, nymphs and adults of insects of the families: Teltigonidae, Gryllidae, Gryllotalpidae, Blattidae, Peduviidae, Phyrrhocoriae, Cimicidae, Delphacidae, Aphididae, Diaspididae, Pseudococcidae, Scarabaeidae, Dermestidae, Coccinellidae, Tenebrionidae, Chrysomelidae, Bruchidae, Tineidae, Noctuidae, Lymatriidae, Pyralidae, Culicidae, Tipulidae, Stomoydae, Trypetidae, Muscidae, Calliphoridae and Pulicidae, as well as Akarida of the families lxodidae, Tetranychidae and Dermanyssidae.

The insecticidal or acaricidal action can be substantially broadened and matched to give circumstances by the addition of other insecticides and/or acaricides.

As additives there are suitable for example the following active substances:

ORGANIC PHOSPHORUS COMPOUNDS Bis-0,0-diethylphosphoric acid anhydride (TEPP) Dimethyl-( 2,2 ,Z-trichlorol-hydroxyethyl )-phosphate (T RICH LORFON) 1,2-dibromo-2,2-dichloroethyldimethylphosphate (NALED) 2,2-dichlorovinyldimethylphosphate (DICHLORVOS) 2-methoxycarbamyll-methylvinyldimethylphosphate (MEVINPHOS) Dimethyll -methyl-2-( methylcarbamoyl vinylphosphate cis (MONOCROTOPHOS) 2-Chlor-5-tert-butyl-phenyl-N-methylcarbamate 4-(Methyl-propargylamino)-3,5-xylyl-N- methylcarbamate 4-(Methyl-'y-chlorallylamino)-3,S-xylyl-N- methylcarbamate 4-(Methyl-flchlorallylamino)-3,S-xylyl-N- methylcarbamate l-( B-Aethoxycarbonylethyl)-3-methyl-5-pyrazolyl- N,N-dimethylcarbamate 3-Methyl-4-(dimethylamino-methylmercaptomethylenimino)phenyl-N-methylcarbamate l,3-Bis( carbamoylthio)-2-(N,N-dimethylamino)- propanhydrochloride S,5-Dimethylhydroresoreinoldimethylcarbamate Z-[Ethylpropargylaminol-phenyl-N-methylcarbamate 2- [Methylpropargylamino] -phenyl-N- methylcarbamate 2- [Dipropargylamino] -phenyl-N-methylcarbamate 4- [Dipropargylamino] -3-tolyl-N-;methylcarbamate 4- [Dipropargylamino] -3,5-xylyl-N-methylcarbamate 2- [Allyl-isopropylaminol-phenyl-N-methylcarbamate 3- [Allyl-isopropylaminol-phenyl-N-methylcarbamate CHLORINATED HYDROCARBONS 'y-hexachlorocyclohexane [GAMHEXANE; LlNDAN:

yHCl-l] l ,2,3,4,5,6,7,8,8-octachloro-3a, 4,7,7atetrahydro 4,7-methylenindane [CHLORDAN] l,4,5 ,6,7,8,8-heptachloro-3a,4,7,7a-tetrahydro-4,7-

methylenindane [HEPTACHLOR] 1,2,3 ,4, l O,l()-hexachlorol ,4,4a,5,8,8a-hexahydroendol ,4-exo-5 ,S-dimethanonaphthalene [ALDRIN] l ,2,3 ,4, l O, l0-hexachloro-6,7-epoxyl ,4,4a,5 ,6,7,8,8aoctahydro-exol ,4-endo-5,o-dimethanonaphthalene [DlELDRlN] 1,2,3 ,4, l O, l0-hexachloro-6,7-epoxyl ,4,4a,5,6,7,8,8a-

octahydro-endo-endo-5,8 -dimethanonaphthalene [ENDRIN] Additionally, several compounds of formula I possess nematocidal properties and can be used, for example, for combating the following plant parasitic nematodes: Meloidogyne sp., Heterodera sp., Ditylenchus sp., Pratylenchus sp., Paratylenchus sp., Anguina sp., Helicotylenchus sp., Tylenchorhynchus sp., Radopholus sp., Belonlaismus sp., Trichodorus sp., Longidorus sp., Aphelenchoides sp.

The compounds of formula I can be used alone or together with suitable carriers and/or additives. Suitable carriers or additives can be solid or liquid and correspond to materials customarily used in formulation technique such as e.g. natural or regenerated materials, solvents, dispersing agents, wetting agents, adhesives, thickeners, binders and/or fertilisers.

For application the compounds of formula I can be processed by means of generally known techniques to dusts, emulsion concentrates, granules, dispersions, sprays, solutions or suspension in the usual way. Cattle dips and spray races, in which aqueous preparations are used should also be mentioned.

The agents according to the invention are manufactured in known manner by intimately mixing and/or grinding active substances of the formula I with the suitable carriers, optionally with the addition of dispersants or solvents which are inert towards the active substances. The active substances may be available and can be used in the following forms:

Solid forms dusts, tracking agents, granules, coated granules, impregnated granules and homogeneous granules. Liquid forms:

a. active substance concentrates which are dispersible in water: wettable powders, pastes, emulsions;

b. solutions.

To manufacture solid forms (dusts, tracking agents), the active substances are mixed with solid carriers. Suitable carriers are, for example: kaolin, talcum, bolus, loess, chalk, limestone, ground limestone, attaclay, dolomite, diatomaceous earth, precipitated silica, alkaline earth silicates, sodium and potassium aluminium silicates (feldspar and mica), calcium and magnesium sulphates, magnesium oxide, ground synthetic materials, fertilisers, for example ammonium sulphate, ammonium phosphate, ammonium nitrate, urea, ground vegetable products, such as corn meal, bark dust, sawdust, nutshell meal, cellulose powder, residues of plant extractions, activated charcoal etc, each used alone or in admixture with one another.

Granules can be very easily manufactured by dissolving an active substance of the formula I in an organic solvent and applying the resulting solution to a granulated material, for example attapulgite, SiO granicalcium, bentonite etc. and then evaporating the solvent.

Polymer granules can also be manufactured by mixing the active substances of the formula I with polymerisable compounds (urea/formaldehyde; dicyandiarnide/formaldehyde; melamine/formaldehyde or others), whereupon a mild polymerisation is carried out that does not affect the active substances and in the process of which the granulation is carried out during the gel formation. It is more advantageous to impregnate finished, porous polymer granules (urea/formaldehyde, polyacrylonitrile, polyester or others) which have a specific surface area and a favourable predeterminable adsorption/desorption ratio. with the active sub stances, for example in the form of their solutions (in a low boiling solvent) and to remove the solvent. Polymer granules of this kind in the form of microgranules having a bulk densitiy of 300 g/litre to 600 g/litre can also be manufactured with the aid of atomisers. The dusting can be carried out from aircraft over extensive areas of cultures of useful plants.

lt is also possible to obtain granules by compacting the carrier with the active substance and carriers and subsequently comminuting the product.

To these mixtures can also be added additives which stabilize the active substance and/or non-ionic, anionic and cationic surface active substances, which for example improve the adhesion of the active ingredients on plants or parts of plants (adhesives and agglutinants) and/or ensure a better wettability (wetting agents) and dispersibility (dispersing agents). Examaples of suitable adhesives are the following: olein/chalk mixture, cellulose derivatives (methyl cellulose, carboxymethyl cellulose), hydroxyethyl glycol ethers of monoalkyl and dialkyl phenols having 5 to 15 ethylene oxide radicals per molecule and 8 to 9 carbon atoms in the alkyl radical, lignin sulfonic acids, their alkali metal and alkaline earth metal salts, polyethylene glycol ethers (car- 5 bowaxes), fatty alcohol polyethylene glycol ethers havyvinyl pyrrolidones, polyvinyl alcohols, condensation products of urea and formaldehyde, and also latex products.

The water-dispersible concentrates of the active sub stance, i.e. wettable powders, pastes and emulsitiable concentrates, are agents which can be diluted with water to any concentration desired. They consist of active substance, carrier, optionally additives which stabilize the active substance, surface-active substances and anti-foam agents and, optionally, solvents.

Wettable powders and pastes are obtained by mixing and grinding the active substances with dispersing agents and pulverulent carriers in suitable apparatus until homogeneity is attained. Carriers are, for example, those mentioned for the solid forms of application. In some cases it is advantageous to use mixtures of different carriers. As dispersing agents there can be used, for example, condensation products of sulfonated naphthalene and sulfonated naphthalene derivatives with formaldehyde, condensation products of naphthalene or naphthalene sulfonic acids with phenyl and formaldehyde, as well as alkali. ammonium and alkaline earth metal salts of lignin sulfonic acid, in addition, alkylaryl sulfonates, alkali and alkaline earth metal salts of dibutyl naphthalene sulfonic acid, fatty alcohol sulfates such as salts of sulfated hexadecanols, heptadecanols, octadecanols, and salts of sulfated fatty alcohol glycol ethers, the sodium salt of oleyl methyl tauride, ditertiary ethylene glycols, dialkyl dilauryl ammonium chloride and fatty acid alkali and alkaline earth metal salts.

Suitable anti-foam agents are silicone oils.

The active substances are so mixed, ground, sieved and strained with the addtivies mentioned above that, in wettable powders, the solid particle size of from 0.02 to 0.04 and in pastes, of 0.03 mm is not exceeded. To produce emulsifiable concentrates and pastes, dispersing agents such as those given in the previous paragraphs, organic solvents and water are used. Examples of suitable solvents are the following: alcohols, benzene, xylene, toluene, dimethyl sulfoxide, and mineral oil fractions boiling between 120 and 350C. The solvents must be practically odorless, not phytotoxic, and inert to the active substances.

Furthermore, the agents according to the invention can be applied in the form of solutions. For this purpose the active substance or several active substances of general formula 1 are dissolved in suitable organic solvents, mixtures of solvents or in water. Aliphatic and aromatic hydrocarbons, chlorinated derivatives thereof, alkyl naphthalenes, and mineral oils alone or mixed with each other, can be used as organic solvents.

The content of active substance in the above described agents is between 0.1 to 95 percent, in which connection it should be mentioned that in the case of application from aircraft or some other suitable means of application, it is possible to use concentrations of up to 99.5 percent or even pure active substance.

The active substances of the formula I can, for example, be formulated as follows:

Dusts The following substances are used to manufacture (a) a percent and (b) a 2 percent dust:

at) 5 parts of active substance -Continued pans o1- talcum 2 parts of active substance 1 part of highly disperse silicic acid 97 parts of talcum.

The active substances are mixed with the carriers and ground.

Wettable Powder The following constituents are used to manufacture an a) 40 percent, b) and c) 25 percent and d) 10 percent wettable powder:

a] 40 parts of active substance 5 parts of sodium lignin sulphonate l part of sodium dibutylnaphthalenesulphonic acid 54 parts of silicic acid 25 parts of active substance 4.5 parts of calcium lignin sulphonate 1.9 parts of Champagne chalk/hydroxyethyl cellulose I mixture (111) 1.5 parts of sodium dibutylnaphthalenesulphonate 9.5 parts of silicic acid 9.5 parts of Champagne chalk 8.1 parts of kaolin; 5 parts of active substance 2.5 parts of isooctylphenoxy-polyoxyethylene ethanol |,7 parts of Champagne chalk/hydroxyethyl cellulose mixture (1:1)

8.3 parts of sodium aluminium silicate 16.5 parts of kieselguhr 46 parts of kaolin; 10 parts of active substance 3 parts of mixture of sodium salt of saturated fatt alcohol sulphates 5 parts of naphthalenesulphonic acid/formal ehyde condensate 82 parts of kaolin.

The active substances are intimately mixed in appropriate mixing device with the adjuvants and ground in corresponding mills and rollers. Wettable powder are obtained which can be diluted with water to suspensions of every desired concentration.

Emulsifiable Concentrates The following substances are used to manufacture a) a 10 percent and b) a 25 percent emulsifiable concentrate:

a) 10 parts of active substance 3.4 parts of epoxidized vegetable oil 13.4 arts of a combination emulsifier consisting of atty alcohol polyglycol ether and calcium alkylarylsulphonate 40 pans of dimethyl formamide 43.2 parts of xylene; b) 25 parts of active substance 2.5 parts of epoxidised vegetable oil 10 parts of an alkylarylsulphonate/fatty alcohol polyglycol ether mixture 5 parts of dimethyl formamide parts of xylene.

(14L! x J t:

Scip. 122-126 6 0,0; 7:1 I

CF 0 3 a 37 0 Scip. 13-117 0 9,3: Terr /P p-ccmac 0 11 0 0 (n|' v3r7s\ P- so 13%: 3 C H5u EXAMPLE 2 A. insecticidal ingest poison action Tobacco and potato plants are sprayed with a 0.05 percent aqueous emulsion (obtained from a percent emulsifiable concentrate).

After the coating has dried, Egyptian cotton leaf worms (Spodoptera liroralis) are settled on the tobacco plants and Colarado potato beetle larvae (Leptinotarsa decemlineata) on the potato plants. The test is carried out at 24C and 60 percent relative humidity.

The compounds according to Example 1 have an ingest poison action against Spodoprera liloralis and Leptinotarsa decemlineata.

B. Systemic insecticidal action To determine the systemic action, rooted bean plants (Vicia fabae) are put into a 0.0l percent aqueous active substance solution (obtained from a l0 percent emulsifiable concentrate). After 24 hours, aphids (Aphisfabae) are placed on the parts of the plant above the soil. The aphids are protected from contact and gas action by means of a special device. The test is carried out at 24C and 70 percent relative humidity. In the above test the compounds according to Example I displayed a systemic action against Aphis fabae.

EXAMPLE 3 Action against Chilo suppressalis Six rice plants at a time of the variety Caloro were transplanted into plastic pots (diameter at the top l7 cm) and reared to a height of about 60 cm. Infestation with Chilv suppressali's larvae (L; 3-4 mm long) took place 2 days after application of the active substance in granule form to the paddy water (rate of application: 8 kg of active substance per hectare). Evaluation of the insecticidal action took place l0 days after application of the granules.

The compounds according to Example I were active in the above test against Chilo suppressalis.

EXAMPLE 4 Sterilised compost earth was homogeneously mixed with a wettable powder containing 25 percent of active substance so that there resulted a rate of application of 8 kg of active substance per hectare.

Yound zucchetti plants (Cucumis pepo) were put into plastic pots with the treated soil (3 plants per pot; diameter of pot 7 cm). Each pot was infected immediately afterwards with 5 Aulacophora femnralis and Pachmoda or Chormphila larvae. The control was carried out 4, 8, l6 and 32 days after depositing the larvae.

At -l00 percent kill after the first control, a fresh infestation with 5 larvae each was carried out in the same soil sample with 3 new zucchetti plants. If the activity was less than 80 percent, the remaining larvae remained in the soil sample until the control immediately following. If an active substance at a rate of application of 8 kg/ha still effected a percent kill, a further control with 4 and 2 kg of active substance per hectare was carried out.

In the above test, the compounds according to Example l displayed action against Aulacophora femoralis, Pachmoda and Chorrophila larvae.

EXAMPLE 5 Action Against Ticks A. Rhi'cephalus bursa In each of the two test series of 5 adult ticks and 50 tick larvae are counted into a glass tube and immersed for l to 2 minutes in 2 ml of an aqueous emulsion from an emulsion series each containing I00, 10, l and 0.1 ppm of test substance. The tube is then sealed with a standardised cotton wool plug and placed on its head, so that the active substance emulsion can be absorbed by the cotton wool.

In the case of the adults evaluation takes place after 2 weeks, and in that of the larvae after 2 days. Each test is repeated twice.

B. Boophilus microplus (larvae) Tests are carried out in each case with 20 sensitive or OP resistant larvae using an analogous dilution series as in the case of test A. (Resistance relates to tolerance of diazinone).

The compounds according to Example I act in these tests against adults and larvae of Rhipicephalus bursa and sensitive and GP. resistant larvae of Boophilus microplus.

EXAMPLE 6 Acaricidal action Phaseolus vulgaris (dwarf beans) have an infested piece ofleaf from a mass culture of Temmychus urticae placed on them l2 hours before the test for the acaricidal action. The occupying mobile stages are sprayed with the emulsified test preparations from a chromatography atomiser so that the spray broth does not run off. The number of living and dead larvae, adults and eggs are evaluated after 7 days under a stereoscopic microscope and the result expressed in percentages. During the interim," the treated plants are kept in greenhouse compartments at 25C.

The compounds according to Example l are active in the above test against eggs, larvae and adults of Terranychus urticae.

EXAMPLE 7 Action Against Soil Nematodes To test the action against soil nematodes, the active substance (in the concentration indicated in each case is applied to and intimately mixed with soil infected with root gall nematodes (Meloidgyne avenaria). lmmediately afterwards, tomato cuttings are planted in the thus prepared soil in a series of tests and after a waiting time of 8 days tomato seeds are sown in another test series.

In order to assess the nematocidal action, the galls present on the roots are counted 28 days after planting and sowing respectively. The compounds according to Example I display good action against Meloidgyne avenaria in this test.

What we claim is: l. A compound of the formula R S X wherein R. is C -C alkyl,

UNITED STATES PATENT AND TRADEMARK OFFICE CERTIFICATE OF CORRECTION PATENT NO. 3,891,728 DATED June 24, 1975 |NVENT0R(5) Jozef Drabek and Denis Varsanyi It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

The following should be inserted in the Heading:

FOREIGN APPLICATION PRIORITY DATA September 30, 1971 Switzerland 14208/71 July 27, 1972 Switzerland 11229/72 Signed and Scaled this Arrest:

RUTH C. MASON C. MARSHALL DANN Arresting Officer (ummissiuner nj'larenrs and Trademarks 

1. A COMPOUND OF THE FORMULA
 2. A compound according to claim 1 wherein R1 is n-propyl R2 is ethyl R3 is trifluoromethyl, R4 and R5 are each hydrogen or chlorine, and X is oxygen.
 3. The compound according to claim 2 